Azo dye and method of making same



Patented Dec. 18, 1934.

1,984,739 v AZO DYE AND METHODYOF MAKINGUSHAMEL Ernest F. Gretna and Lindley 1vrius",'Mid1aiia. Mich., assignors to ThcDovv Chemical -Com-. I

pany, igan Midland, Mich., a corporation of 'Mi ch:

No Drawing. Applicatienznpril 3,1981,

Serial No. 530,426

- new This inventionrelates to direct developed azo dyestuffs of the type wherein an arylide of 2,3- hydroxy-naphthoic acid is coupled with a diazotized arylamine, and has regard particularly to a .5 new sub-class of the above'general character, but

distinguished from those hitherto known in that the aforesaid arylidecomponent thereof is formed bycondensingaromatic amines having probably the general formula wherein X represents a halogen group, R and R.

represent alkyl, aryl and/ or aralkyl residues, and v Ri'represents an arylresidue of the benzene or naphthalene series which may be further-sub? stituted by groups such as the alkyl, aryl, aralkyl, alkoxy, aryloxy, aralkoxy, benzoyl-amino, halogen; azoand/ornitro groups.

It iswell known that direct azo-dyes fast to light and washing are produced by coupling" ary-lides of 2,3-hydroxy-naphthoic acid with di'-.= azotized or-,tetrazotized arylamines, asis evidenced byitheglarge number of issued patents bearing ;on, the subject. -We have discovered, however, that when the di-alkoxy-halo-anilides or di-aryloxy-halo-anilides of '2,3-hydroxynaphthoic acid are so coupled, the dyestuffs pro-v duced are fast toward light and washing and the colors produced are deep and. clear in tone. The invention, then, consists of azo dyestuffs derived from; di-alkoxy-halo-anilides and di-aryloxyhalo-anilidesof 2.3-hydroxy-naphthoic acid, together with methods for the preparation thereof, as. hereinafter fully described and particularly pointed out in the claims, the following descripe varying rom r b u and b ack Wai le r and br'illiant' tones. -They are-best prepared by developing on the fiber, but'may also be produced insubstanc'e 'per seor deposited -upon"suitablesubstrata 'toformilakesgin which forms they are useful pigments because of their insolubility, sta-' bility and fastnessi Substituted anilines, from which the arylides hereinafter utilized were made, were themselves prepared in the following way:j

Ortho-dichlorobenze'ne was. chlorinated to obtain trichlorbenzene and the latter, nitrated, either with concentrated nitric acid or with a mixture of nitric and sulfuric acids, to the corresponding trichlor mono nitro-benzene of M; P. 57 C-.,-and having probably the formula I "com was formed by treating a boiling methyl alcohol solution o'f-the. above mentioned trichlor-nitrobenzenew'ith slightly. more than vtwo molecular equivalents of sodium or potassium hydroxide dissolved in methyl alcohol. The mixture was diluted with a. large excess. of water, filtered, and

' the residue recrystallized frommethanol, M. P.

Chloro-diethoxy-nitro-benzene" ofyM. P. 120.5 C. was prepared-inthe same jmanner'; as was chloro-methoxy nitro-benzene, except that ethyl alcohol was used in place of methyl alcohol.

Chloro-diphenoxy-nitrobenzene of M. P. 735 C. was prepared by treating a mixture of potassium or sodium phenolate with trichloro-nitrobenzene atapproximately 220 C.for 4 hours. The product was distilled and the fraction dis tilling at210-215 C. at 1 mm.collected.

The:chloro-dialkoxy-nitro-benzenes and chloro-diphenoxy-nitro-benzene were reduced with iron and acetic acid tothe corresponding sub- I stituted anilines according to the known rnethod.

A preferred manner in,which dyes comprising the invention may be prepared is illustratediin the specific examples given below, it being understood, howeventhat such examples are not to be construed as a limitation upon the invention.

. Example 1 The di-ethoxy chlor-anilide of 2,3-h'ydroxynaphthoic acid is prepared by heating equimolecular quantities of di-ethoxy-chlor-aniline and 2,3-

hydroxy-naphthoic acid inthe presence of approximately 15 per cent of their combined weight H (slightly more than of a molecular equivalent) of phosphorous trichloride under reflux and in a medium of toluene for 3'to 5 hours. Excess sodium carbonate is then added and the toluene removed by distilling with steam.. The aqueous residue containing the arylide product in'susproduced has probably the formula 1 Cotton material is impregnated with a slightly alkaline solution of the above arylide to which may be added advantageously, but not necessarily, formaldehyde and a fixative, such as Turkey red oil or an aluminum salt. {The material is then dipped in a cold solution of sodium acetate or carbonate, and the dye is developed by adding a diazo solution derived from 4-methoxy-3-chloraniline. The color developed is a clear, dark cardinal. The dyestuff has probably the formula Example 2 By procedure similar to that described in Example l, the di-methoxy-chlor-anilide of 2,3- hydroxy-naphthoic acid was prepared by condroxy-naphthoic acid. The dye is degeloped by treatment with a diazo solution-i fi'dmsorthoamino-diphenyl ether. The color is a castilian red. The dyestuff has probably the formula OONH com 15 OCH:

Example 3 g The di-phenoxy-chlor-anilide of 2,3-hydroxynaphthoic acid is prepared in the manner described in Example 1. The dye is developed by N treatment with a diazo'solution from 4,4'-diam- 25 ino-diphenyl ether. The color developed is a strawberry red. The dyestufi has probably the formula 1 on I n I In like manner, we have prepared other dyes of the same general type, for example, those shown in the following table, the color of the dyes 15 being designated according to the Standard Color Card of America, (1928 ed), issued by The Textile Card Association of the United States, Inc. I n While in the detailed'E'xample 1 cotton fiber 50 has been specifically referred to as the material to be dyed with the herein described new dyestuffs, other natural or synthetic fibers may likewise'be dyed therewith, such as silk, rayon or the W like. It is immaterial as regards the novelty or 55 our invention whether the dye is applied by developing on the fiber or prepared in substance for use as'a pigment. Mordanting or other auxiliary treatments for promoting the absorption of the dye by the fiber, or after treatment with metallic salts, e. g. chromium, copper or aluminum salts, for fixing the dye or modifying itscolor tone may be optionally employed without departing from the spirit of our invention, which is intended to include not only the dyestuffs of the general type herein described, but also material dyed there densing di-methoxy-chlor-aniline with 2,3-hywith.

Arylide component Diazo component Color I -70 zfihgldtoxymaphthoic acid condensed (lhloro-dimethoxyenilme m-nittaniline Pimento. D 2-ch1or-4-nitmniline Goya.

o-amino-diphenyl ether Castilian red.

3,4-dicl1loro-ani1ine Pimento. i-phenoxy-alpha-naphthylminn Mulberry fruit.

Arylide component Diazo component Color 2,3-htyfilroxy-naphthoic acid condensed Chloro-dimethoxy-aniline... Dianisidine Homage blue. D 4,4'-diamino'dipheny1 ether Cardinal. D Alpha-naphthy Claret. Chlorom-(benzoyl-amino-) aniline Cestilian red. D m-nitranlline Lacquer.

Trichlnmnili'na D0. 2-chloro-4-amino-diphenyl ether Goya. p'nitro-oi Lacquer. 3,4-dichloro- Do. o-amino-diphenyl h r I Scarlet. 2amino-4,5-dichloroT-phenyl-dmhenyl other Cardinal. 2-amino-4,6-dichloro-dipheny1 ether Goya. 2-methoxy-3-chloro-5-amino-diphenyl Do. o-chloro-p Lacquer. 2,2-diamino-4,4-dibromo-diphenyl ether Goya. 2-nitro-4-methyl-aniline Do. 3-011101'0-4-meth0xy-nnilinn Dark cardinal. 4,4'-diamino-diphenyl ether Do. 2-methoxy-3,ediamino-diphenyi Garnet. 4-(benzoyl-amino) aniline Dp. 2,4-diethoxy-5-chloroamlin Redd1sl1 garnet. 4-amino-azo- Garnet. Alpha-naphthy Reddish claret. z-methoxy-aamino diphenyl Maroon. l-aminc-5,8-dich1oro-naphthalene Raspberry. 2,7-diamino-3,fi-dibromo carbazoleun-.. Light mulberry. l-amino-i-(benzoyl-amino) naphthalene- Reddish plum. Amino-naphthyl-phenyl ether Do. Amino-l,2-dinaphthyl other Mulberry fruit. 2,2'-dimethoxy-3,3-diamino-1,1-d1naphthyl Do. LE-diamino- Egg plant. l-aminoi-naphthalene-az0-3-chloro-4-methoxy-benzene Bluish black. Benzene-azo-i-naphthyl-amine Do. 0 l-nitro-4-ethoxy- D Ohloro-diphenoxy smih'm m-nitraniline Coral blush.

o 2chloro-4-nitran1line Fiesta.

o-amino-diphenyl ether Do. 3,4-dichloro-aniline-... Crab apple. Amino-naphthyl-phenyl ether Mignon. Dianisidine- Taupe. 4,4-diamino-diphenyl ether Strawberry. Alpha-naphthyla Raspberry.

In the following claims it is understood that the invention comprehends the coupling of the herein described arylides of 2,3-hydroxy-naphthoic acid with any diazotized aromatic mono-, di-, or poly-amino compound, as well as the azo-dyestuffs derived therefrom.

Other modes of applying the principle of our invention may be employed instead of the one explained, change being made as regards the materials employed, provided the ingredients stated by any of the following claims or the equivalent of such ingredients be employed.

We therefore particularly point out and distinctly claim as our invention:

1. The method of making an azo dye which comprises coupling an arylide of 2,3-hydroxynaphthoic acid, having the formula.

on x v v o o NHQO 02H;

wherein X represents a halogen group, with a. diazotized aromatic amino compound.

2. The method of making azo dyestuifs which comprises coupling an arylide of 2,3-hydroxynaphthoic acid having the formula witha diazotized aromatic amino compound.

3. An azo dyestuff having the formula on x OONHQO 01m 03H! wherein X represents a halogen group and R represents an aromatic radical from a diazotized aromatic amino compound.

4. An azo dyestuff having the formula OH 01 OONH-GQ-(LHI 

